Molecular columnar discotics

Recent work focuses on non-classical mesogenes which are built up by self-assembly. One example is a family of polymers containing disk-like groups which form no liquid crystalline phase, but ean act as an electron acceptor or donor. Charge transfer complexation with a complementary low molecular mass compound induces nematic or columnar discotic liquid crystalline order [153,154]. Figure 13 demonstrates this with the example of a polyester, bearing electron-rich tetra(alkoxy)tri-phenylene-units in the main chain, mixed with the electron deficient aromatic 2,4,7-trinitro-9-fluorenone (TNF). While the pure polymer shows a non-ordered isotropic melt, a columnar phase appears on addition of TNF. 

Chandrasekhar S 1998 Columnar, discotic, nematic and lamellar liquid crystals Their structures and physical properties Handbook of Liquid Crystals Vol 2B. Low Molecular Weight Liquid Crystals I ed D Demus, J Goodby, G W Gray, H-W Spiess and V Vill (New York Wiley-VCH)... 

Keywords Columnar mesophase. Structure, Interactions, Molecular architecture, Discotic... 

A new class of hexabenzocoronene derivatives, e.g. compounds (Scheme 7.13) can self-organize into liquid crystalline phases composed of molecular stacks that orient spontaneously parallel to the surface [177, 178]. Field effect transistors based on these materials show high charge-carrier mobilities, high on/off ratios, and low tum-on voltages. So far compound 44 exhibits the best field effect transistor properties achieved for a columnar discotic material. Polarized fight microscopy revealed that these materials tend to orient their columns parallel to the surface upon thermal annealing. 

B. Brandi, J.H. Wendorff, Eutectic mixtures with plastic columnar discotics molecular structure, phase morphology and kinetics of phase separation. Liq. Cryst. 32, 553-563 (2005)... 

Cyclic hydrocarbons with six equivalent substituent chains emanating from several carbon atoms about the ring can again adopt conformations in which the molecular shape is disk-like, but the aspect ratio is much larger. If the chains are somewhat flexible and the molecules possess an appropriate balance between order and disorder and attractive and repulsive intermolecular forces, the creation of new mesophase types can be envisioned - and several have been found [102,104]. The two general classes of aggregation in liquid crystalline phases of discotic molecules are lenticular nematic (N ) and columnar discotic (D) [100-104]. Carbonaceous pitch mesophases, discussed in section 1.4.5, resemble phases. Only those discotic mesophases with benzene, cyclohexane and shape-related cores having primarily alkyl chains as substituents will be discussed here. 

We start by reminding ourselves that columnar discotic liquid crystals are comprised of disordered stacks (1-dimensional fluids) of disc-shaped molecules arranged on a two-dimensional lattice (Fig. 1) [1]. This structure imparts novel properties to these materials from which applications are likely to stem. One such property is the transport of charge along the individual molecular stacks [2-7]. The separation between the aromatic cores in, for example, the hexa-alkoxytriphenylenes (HATn), the archetypal columnar discotic mesogen, is of the order of 0.35 nm, so that considerable overlap of n orbitals of adjacent aromatic rings is... 

Another class of liquid crystal materials that has been studied extensively is the discotic liquid crystal. As the name implies, these phases form from disk-shaped molecules. A material showing this behavior was first identified and studied in 1977 by Chandasekar. Examples of some typical discotic molecular structures are shown in Figure 2.19. There are two main classes of discotic phase, the nematic and columnar discotic phases schematics of these phases can be seen in Figure 2.20. The nematic discotic... 

Liquid crystal phases are anisotropic, and the c director is used to indicate the direction of molecular orientation. In the case of the (a) columnar discotic, (b) nematic, and (c) smectic C phases, make a sketch of the molecular arrangement and indicate the c director. 

Other liquid crystal phases composed of molecules having unusual molecular shapes are also known. Some compounds form a cone or bowl shape. These materials are often referred to as bowlic, and some typical examples are hexasubstituted tribenzocyclonones and aza-crowns (17), molecules of which stack on top of each other to form an ordered column which may have anomalous electrical conductivity. When a disklike molecule is divided by a rod-shaped spacer, the molecule (18) is referred to as a phasmid. It exhibits phases bearing some resemblance to columnar discotics. 

NMR spectroscopy can provide valuable information on the structure of mesophases. The most commonly used method for this is the analysis of line shapes in spectra of various nuclei, and, in particular, of H. For a large number of mesophases, NMR spectra are motionally averaged and the spectral line shape reflects the phase symmetry. Line shape analysis of NMR spectra has been employed successfully to investigate the molecular organization and tilt angle of smectic C phases, as well as the structure of columnar discotic phases and it has been shown to be more sensitive than optical techniques to some aspect of biaxial ordering. Moreover, this technique has been shown to be extremely helpful in the discrimination of lyotropic phase symmetry. As examples, NMR spectra of some lyotropic phases are reported in Figure 4. 

As discussed in Chaps. 3 and 4, (columnar) discotic liquid crystals are oriented in columns separated by molten aliphatic chains and, consequently, they can conduct charge efficiently along the channels in one dimension. The organization of the different phases is described elsewhere [19, 20] and the efficiency of charge transport can be directly related to the short intermolecular spacing and order of different types of mesophase, with few exceptions [21]. For example, hole mobility is higher in ordered, rather than disordered, columnar phases and even higher in helically-ordered phases where molecular rotation is suppressed about the columnar axis [22], Some mesomorphic derivatives of hexabenzocoronene, for example hexaphenyl-substituted hexabenzocoronene (HBCn, see Table 8.2 for chemical structures of all discotic materials discussed here) have hole mobilities... 

Most polymeric Hquid crystals are based on stiff rod-like molecular units which are called calamitic mesogens. There are some unusual polymers (which are not discussed here) that contain flat disk-like molecular units called discotic mesogens in which the disks form columnar arrays like stacks of poker chips. 

The prime requirement for the formation of a thermotropic liquid crystal is an anisotropy in the molecular shape. It is to be expected, therefore, that disc-like molecules as well as rod-like molecules should exhibit liquid crystal behaviour. Indeed this possibility was appreciated many years ago by Vorlander [56] although it was not until relatively recently that the first examples of discotic liquid crystals were reported by Chandrasekhar et al. [57]. It is now recognised that discotic molecules can form a variety of columnar mesophases as well as nematic and chiral nematic phases [58]. 

Figure 8.3 Schematic representation of the molecular arrangement in the nematic discotic (Nq), columnar nematic (Ncoi), columnar hexagonal (Coin), and columnar rentangular (Coir) mesophases. A tablet represents a molecule with disk-like shape.

Nuckolls and Katz have synthesized discotic liquid crystalline molecules in which the core is a helix in its own right.37 Nonracemic helicene 33 was found to assemble into a columnar mesophase in which the helicenes stack on top of each other. CD spectroscopy showed a strong increase of the Cotton effect upon going from the molecularly dissolved state to the aggregated state, exhibiting an amplification of chirality. These helical columns give rise to a strong expression of chirality because the intrinsic shape of the helicenes... 

Discotic LC are formed by disk-like molecules with aromatic cores and side chains that are either hydrophobic (i.e., thermotropic) or hydrophilic (i.e., lyotropic). The discotic nematic (No) phase behaves like a normal nematic phase formed by rod-like molecules, and the disk-like molecules are oriented with their short molecular axes parallel to the director but show no positional order. More ordered columnar phases are commonly formed by thermotropic discotics. The two-dimensional structure can pack the columns into a hexagonal or rectangular columnar phase, while within the columns, disks can be... 

PAH chemistry is of practical as well as theoretical interest. PAHs can be regarded as well defined subunits of graphite, an important industrial material, which is so far not totally understood at the macroscopic level. In this context, it is our aim to delineate the molecular size at which the electronic properties of PAHs converge to those of graphite. Furthermore, alkyl substituted derivatives of hexabenzocoronene (HBC) form discotic mesophases and, therefore, provide opportunities for materials which allow one-dimensional transport processes along their columnar axis [83,84]. Their application for photovoltaics and Xerox processes is also of current interest. 

The discotic phases can show also a complex polymorphism. Nematic and cholesteric-like, low viscosity phases have been reported recently. In these, the director vector is perpendicular to the plane of alignment of the flat molecules56) in contrast to the normal nematics and cholesterics where it is parallel to the molecular axis. Most frequently, however, discotics form columnar arrangements as shown in Fig. 10. The order within the columns may change from liquid to quasi-crystalline. The columns are then packed in hexagonal or tetragonal coordination, but are free to slide in the direction parallel to their axes S7). The viscosity of these more ordered discotics is considerably higher than the nematic discotics. 

In discotic phases the orientation of the molecules is perpendicular to the molecular plane. Here, the columns can be arranged in a nematic or columnar manner. In the nematic phase the molecules possess a centre of gravity randomly ordered, but with the short molecular axis of each molecule more or less parallel. In the columnar phase, beside the preferable orientation of the short molecular axes, the disc-like molecules are ordered forming columns. Depending on the correlation strength between he columns these phases can be subdivided into ordered or disordered. A third possibility is to have a thermodynamically preferable position of the columns in the mesophase, like in a hexagonal cell. Additionally, a tilt of the columns is also possible. 

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